Vat dyestuffs and process of preparing them



Patented @ct. 6, 1931 UNETED STATES 1,825,749 PATENT OFFICE GEORG KRANZLEIIT, HEINRIGI-I VOLLIVIANN, AND MARTIN CORELL, OF FRANKFORT-ON- THE-MAIN-HOCHST, GER-MANY, ASSIGNOB S TO GENERAL ANILINE WORKS, INCL, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE VAT DYESTUFFS AND PROCESS OI PREPARING THEM No Drawing. Application filed February 25, 1929, Serial No. 842,661, and in German March 23, 1928.

3 tainable by causing halogen dibenzpyrenquinones, containing at least one halogen in the molecule and havmg the following general formula:

wherein R stands for the bivalent residue to act upon nitrogen-containing compounds, having at least one exchangeable hydrogen atom, of the following general formula: R -l-TI-IR wherein R stands for hydrogen or a monovalent' organic residue, R stands for a substituted or non-substituted aromatic residue or R and R together stand for a phthaloyl-residue.

The reaction is carried out in the presence cf a solvent as for instance nitrobenzene, ortnocresol, naphthalene, quino-line, while adding an acid-binding agent as for instance sodium acetate, sodium carbonate or the like, furthermore in the presence of a copper-catalyst as for instance copper powder, copper oxide and copper salts as for instance copper chloride or copper acetate.

; The products thus obtainable are compounds of the following general formula:

wherein R stands for the bivalent residue f R2 wherein R stands for the bivalent residue I R represents hydrogen or NH. benzoyl, and X stands for hydrogen, the COOH or the CH0 group.

Structural formulae of other compounds are given in the following specific examples.

Tints and fastness properties of the substances prepared according to the above described process may be changed by treating them with an acid condensing agent, such as aluminium chloride, sulfuric acid, chlorosulfonic acid, the condensation being carried out if required in the presence of a melting agentas for instance sodium chloride.

The following examples serve to illustrate our invention but they are not intended to limit it thereto, the parts being by weight.

1. 82 parts of monobromisodibenzpyrenquinone, obtainable by treating 2-(para-bromobenzoyl) -benzanthrone with aluminium chloride while passing oxygen into the melt, are heated to boiling temperature for about 5 hours with a mixture of {l5 parts of a-aminoantllraquinone, E parts of sodiunracctate, and 7 parts of copper acetate in 1500 parts ofi nitrobenzene. The conversion-product. separating in a or stalline form while the mass is boiling, is filtered by suction. It has the following probable formula:

It forms a dark-violet powder which dissolves in concentrated sulfuric acid to aelloWish- 'reen solution. cotton from an orange-red vat dull' red tints.

By treating the reaction product thus obtained at about 130 C. for half an hour with ten times its weight of sodiu1naluminium chloride, there is obtained after decomposition of the melt a dyestutl which dyes cotton from a red vat reddish-brown tints of a good fastness to washing and chlorine.

2. parts of monobromisodibenzpyrenquinone, obtainable as indicated in Example 1, are heated to boiling temperature for some hours with 15 parts of anthranilic acid, 5 parts of anhydrous sodium carbonate and 2 parts of copper acetate in 600 parts of orthocresol. The new compound isolated from the mass as described in the preceding example dissolves in concentrated sulfuric acid to a pure yellowish-green solution and dyes from a yel owish-red Vat claret-red tints. It has the following probable formula:

by treating isodibenzpyrenquinone with a quantity of bromine sufficient for introducing The dyestufl yes two bromine atoms, with parts of (XilInlllO' anthraquinone, 40 parts of sodium acetate and 3 parts of: co per acetate in 800 parts of nitrobenzene, a yestuif is. obtained, which dissolves in concentrated sulfuric acid to a green solution and which dyes cotton from a red. vat intense violet tints. It probably corresponds to the following formula:

4. 25 parts of monochlor 3.4.8.9-dibenzpyrenquinone obtainable by causing benzylchloride to act upon 5 chlbrbenzanthrone in the presence of aluminium chloride according to the process described in the U. S. Patent No. 1,564,584, dated December 8, 1925, in the name of Georg Kriinzlein, Martin Corell and Robert Sedlmayr, are heated to boiling temperature for 18 hours with 30 parts phthalimide, 10 parts of sodium acetate and 2.5 parts of copper powder in 500 parts of nitrobenzone. The product is filtered cold by suction, washed with alcohol and subsequently with water. The phthalimidodibenzpyrenquiname of the following. probable formula:

German patent specification Nu. l30556, are

(3. By condensing in'the same manner tetrachlor dibenzpyrenquinone with oc-flIlJlIlO- anthraquinone, a product of the probable formula:

coo no is obtained which dyes from a violet-red vat bluish-black tints. It dissolves in concen' trated sulfuric acid to a red solution.

7. By condensing tetrachlordibenzpyrenquinone with anthranilic acid (1 mol.) in the manner described in Example 2, a dark'green '1' dyestuff of thefollowing probable formula:

' minium chlorideor chlorosulfonic acid anotherdyestufl is obtained which dyes from a violet-red vat intense brown tints.

' 8. 100 parts of dibromisodibenzpyrenquinone, obtainable as indicated in Example 3, are heated to boiling temperature-for 12 hours with parts of benzamide, 20 parts of "anhydrous sodium carbonate and 5' partsof copper acetate in 600 parts of nitrobenzene. The mass is filtered cold by suction and washed with alcohol and water. The darkviolet product thus obtained dissolves in concentrated sulfuric acid to a yellowish-green solution. The dyestuff dyes cotton from a reddish-orange vat violet tints. It probably corresponds to the following formula:

By treating in an analogous manner the monochlorodibenzpyrenquinone mentioned in Example 4, the monobenzoylamino derivative is obtained which dyes cotton clear and fast scarlet tints. y

9. By fusing 10 parts of the bluish-black dyestuff obtained (according to Example 6) with parts of sodium-aluminium chloride at a temperature of from 120 C. to 130 C. until the coloration of the fusion has turned from red to pure blue and afterwards working up the product, adyestuif is obtained which dissolves in concentrated sulfuric acid to a pure blue solution and which dyes cotton from a violet vat an intense fast brown tint.

10. 24.5 parts of dibrom dibenzpyrenquinone of the following formula: 7

6.7 parts of l-amino 'anthraquinone-2 carboxylic acid, 6 parts of sodium acetate and 5 parts of copper acetate are heated to boiling temperature in 300 ccm of nitrobenzene until the sparingly soluble reaction product has been separated. The dyestult thus formed is filtered by suction at 100 (3., washed with hot nit-robenzene and subsequently isolated in the usual manner. It has the following probable formula:

pure red solution. It dyes from a violet-blue vat an intense reddish-brown tint.

12. 10 parts of (llbl'OllllSOdlll6l1ZPyl0ll quinoue, 28 parts of 1-amino-d-benzoylaminoanthraquinone, 5 parts of sodium carbonate, 2 parts of sodium acetate and 3 parts of copper chloride are maintained at boiling temperature in 250 parts of naphthalene for 18 hours, poured hot into 1 liter of nitrohenzcne, heated to 100 C., filtered by suction at about 80 C., washed with a small quantity of nitroben- Zene, boiled out with xylene and isolated as usual. The dyestullldissolvcs in concentrated sulfuric acid to a yellowish-green solution and dyes cotton from a brmvnish-rcd vat bluish-gray tints of good fastness properties. It probably has the following formula:

I ll

I II

OC-Co'lh \Ve claim;

1. The process which comprises heating .5 It dinsolves in concentrated sulfuric acid to a at boiling temperature a compound having 5 at least two bromine atomsin the molecule of the following formula: g I

with a compound of the following formula:

in the presence of nitrobenzene, sodium acetate and copper acetate. 1

:2. The process which comprises heating a compound havingat least onehalogen atom in the molecule of the following formula:

wherein R stands for the bivalent residue wherein R stands for thebivalent residue with a compound ofthe following formula? O N135:

H R 0 wherein X stands for hydrogen, the

' o o c or the g and R for hydrogen, or the NH.aroyl group, in the presence of nitrobenz'ene, sodium acetate and copper acetate and treating the resulting product with molten sodium-aluminium chloride. 7

4. The process which comprises heating a compound having at least one halogen atom in the molecule of the folowing formula:

with a compound of the following formula: R NHR wherein R stands for hydrogen 1 or a monovalent organic residue, R stands for an aromatic residue which may be substituted or not or R and R together stand for phthaloyl-residue, in the presence of nitrobenzene, sodium acetate and copper acetate and subsequently treating the resulting product with an acid condensing agent.

5 The process which comprises heating a compound having at least one halogen atom in the molecule of the following formula:

with a compound of the following formula: V 8. As new products, compounds of the following formula;

a R wherein X stands for hydrogen, the O o o f I t group R1 NH and R for hydrogen, or the NH.aroyl group, o X in the presence of nitrobenzene, sodium ace- NH tate and copper acetate and subsequently Y 80 treating the resulting material with molten andium'aluminium chloride.

6. As new produets,oo1npounds of the following general formula: wherein R stands for the bivalent residue 8 x NHR and X for hydrogen, the COOH or the CH0 X X group.

9. As new products, compounds of the fol lowing formula:

wherein R stands for the bivalent residue x- Nrm R, for aryl or aroyl and X for hydrogen or NH R,

7. As new products, compounds of the following formula: i x- (/I 0 -21 105 RI wherein R- stands for aryl or aroyl and X -R1 NH stands for hydrogen or NHR.

\ \0 10. As new products, compounds of the following formula o r 0 \R 11:;

Nu \O as X 120 \0 wherein R stands for the bivalent residue O R for hydrogen, group or NI-Lbenzoyl, X for hydrogen, the COOH or the CH0 group. wherein R stands for, hydrogen or NH.ben-

Zoyl and X stands for hydrogen, the COOH or the CH0 group.

11. As new products, compounds of the following formula:

wherein X stands for the COOH or the CH0 group.

12. As a new product, the dyestufl of the following formula:

dissolving in concentrated sulfuric acid to a ".5 pure red solution and dyeing from a, violetblue vat an intense reddish-brown tint.

In testimony whereof, We EtffiX our signatures.

GEORG KRANZLEIN. t HEINRICH VOLLMANN.

MARTIN CORELL.

CERTIFICATE OF CORRECTION.

Patent No. 1,825,740. Granted October 6, 1931, to

GEORG KRKNZLEIN ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, line 130, for the numeral "6.7" read 2.6.7; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th day of February, A. D. 1932.

M. J. Moore,

' (Seal) 7 Acting Commissioner of Patents. 

